Mono-oxamic acids of 4.4&#39;-diaminodlarylcyclohexane compounds



Patented Jan. 20, 1931 UNITED STATES GEORG KALISCHER, OF FRANKFQRT-ON-THE MAIN, AND RICHARD FLEISCHHAUER, F

ERANKFORT-ON-THE-MAIN -FEcHENl-IElM,

GERMANY, ASSIGNORS T0 GENERAL ANILINE woaxs, 11m, or EW'YORK, n; Y., AooRroRATIoN or DELAWARE MONO-OXAMIC ACIDS OI 4.4;-DIAMINODIABYLCYGLOHEXANE COMPOUNDS No Drawing, Application filed August 22 1928, Serial 110.387,?88, and in Germany August 28, 1928.

We have found that mono-oxamic acids of 4.4-diamino-diaryl-cyclohexane compounds which correspond to the general formula:

NH-OOGOOH HEKH I (wherein one X means hydrogen or methyl,

the other Xs l1 drogen and the Ys stand for hydrogen, ha ogen, methylor alkoXygroups) are obtained by treating with oxalic 0 acid 4.4-diamino-diaryl-cyclohexane compounds which are described in U. S. application Serial No. 252,941, filed February 8, 1928, and correspond to the general formula:

NH: 25 o Y (wherein X and Y have the above signification).

According to our process the starting bases are heated with oxalic acid until they have mostly disappeared. Advantageously this reaction is carried out in the presence of'a' solvent, as water or an inert organic solvent, care being taken that the quantity of the oxalic acid applied does not substantially surpass that necessary for dissolving the bases.

The mono-oxamic acids are diflicultly soltioned therein.

stood that we are not limited to the particular conditions nor to the specific products men- Ezvample 1 13.3 parts of 4.4 -diamino-diphenyl-1.1 cyclohexane, obtainable-by condensing 1 molecule of cyclohexanone with 2 molecules of aniline, are boiled under arefiux condenser with 400 parts of water and 13.6 parts of crystallized oxalic acid. From the originally clear solution the formed oxamic acid precipitates gradually as a heavy powder. When its quantity no more increases and the base applied hasnearly disappeared, the precipitate is filtered hot and washed with water. For purification it is dissolved at (SO- in a dilute ammonia solution, filtered'if necessary from small amounts of impurities and again precipitated therefrom While warm by means of an acid.

The new mono-oxamic acid corresponds to the formula:

li'auzmplev 2 14.7 parts of 4.4-diarnino-3.3-dimethyldiphenyl-cyclohexane, 16' parts of crystal.-

lized oxalic acid and 400 parts of water are boiled for about 2e hours. The mass is worked up as described in Example 1. The new t-amino-3.3-dimethyl-diphenyl-cyclohexane-t-oxamic acid thus obtained corresponds to the formula: I

H2 Hi NH:

'"-methyl-cyclohexane and oxalic acid. It

corresponds to the formula NiHz ONH-c 0-0 0 OH Example 3 Hz H:

16.3 parts of 4A-diamino-3.3-dimethoxydiphenyl-cyclohexane, 17 parts of crystallized oxalic acid and 400 parts of water are boiled for about 24 hours. Then the mass is worked up as described above. The new 4- amino-3.3-dimethoxy-diphenyl-cyclohexanelf-oxamic acid thus obtained corresponds to the formula:

0 CH3: E E O NH 2 H2- \ONHO 0-0 0 on I H2 2 O CH:

It represents a light grey to colorless powder, easily soluble in ammonia solution and in cyclohexanone, diflicultly soluble in alcohol, insoluble in water. hen heated above 200 it decomposes while becoming brown.

Likewise 4.4 diamino-3.3' diethoxy-diphenyl-cyclohexane yields e-amino-3.3-diethoxy-cyclohexane-4-oxamic acid which shows similar properties.

Emample 4 4. 1 -diamino-3.3 -dichloro diphenyl-cyclohexane is treated with oxalic acid in the man'- ner described in the foregoing examples. Thereby i-amino8.3-dichloro-diphenyl-cyclohexane-a oxamic acid is obtained which corresponds to the formula:

It shows similar properties as the products of the foregoing examples.

In an analogous manner 4-amino-3.3-dibromo-diphenyl-cyclohexane-t-oxa1nic acid is obtained bylstarting froin lae diamino- 3.3-dibromo-diphenyl-cyclohexane.

' Example 5 l3parts of crystallized oxalic acid are added to a solution of 13.3 parts of 4.4-diaminodiphenyl-cyclohexane in 50 parts of monochloro-benzene and the mixture is heated under a reflux condenser for some hours} Then the solvent is removed by steam distillation, the remaining mass is dissolved in a dilute ammonia solution"and filtered. From the filtrate 4-amino-diphenyl-cyclohexane-4-oxamic acid is precipitated by the addition of hydrochloric acid. It'is identicalto the prod- V uct of Example 1. We claim V 1. A process which comprises treating a 4. l--diaminodiaryl-cyclohexane compound of the general formula;

Hz H2 NH: XH

I ONm XH X11 1 (wherein one X means hydrogen or methyl, the other Xs hydrogen and the Ys stand for hydrogen, halogen, methylor alko-xy-' groups) with oxalic acid.

2. A process which comprises treating a 4.4-diamino diaryl-cyclohexane' compound of the general formula:

x11 NH:

XH XH (wherein one X means hydrogen or methyl, the other Xs hydrogen and the Ys stand for hydrogen, halogen, methyl or alkoxy groups) with oxalic acid in the presence of a diluent 1 until the base has mostly disappeared.

3. 'A process which comprises treating a 4.4-di aminodiaryl-cyclohexane compound of the general formula NH, H H

(wherein one X means hydrogen or methyl, the other Xs hydrogen and the Ys stand for hydrogen, halogen, methyl or alkoxy groups) with oxalic acid in the presence of water until the base has mostly disappeared, care be- 7 ing taken that the quantity of the oxalic acid applied does not substantially surpass that necessary for dissolving the base applied.

4. As new compounds the mono-oxamic acids of 4.4-diamino-diaryl-cyclohexane compounds corresponding to the general formula NH-OO-COOH (wherein one X means hydrogen or a methyl group, the other Xs hydrogen, the Ys stand for hydrogen, halogen, methyl or alkoxy groups), which compounds are nearly white substances, difficultly soluble in water and in organic solvents, forming sodium, and potassium salts which are difficultly soluble in cold water, more soluble in hot water, capable of being diazotized and yielding by saponifying agents 4.4-diamino-diaryl-cyclohexane compounds.

5. As a new compound 4-amino-3.3-dimethyl-diphenyl-cycloheXane-t'-oxamic acid of the formula:

NH: H:-

QNIL-C oooon Hz which compound is a nearly White substance, melting when recrystallized from alcohol at about 216, difiicultly soluble in Water and in organic solvents, forming sodium and potassium salts which are difiicultly soluble in cold water, more soluble in hot Water, capable of being diazotized and yielding by saponifying agents 4.4-diamino-3.3-dimethyl-dipl1enylcyclohexane. v

In testimony whereof, We afiix our signatures.

enoae KALISGHER. RICHARD FLEISGHHAUER. 

